Antioxidative preparations

ABSTRACT

An antioxidative composition containing: (a) an active component selected from the group consisting of (i) at least two extracts selected from the group consisting of  Vaccinium myrtillus, Trifolium pratense, Vitis vinifera  and  Thea vinensis;  (ii) at least two active components selected from the group consisting of anthocyanosides, isoflavone glucosides and polyphenols; and (iii) mixtures thereof; and (b) a co-active component selected from the group consisting tocopherol, ascorbic acid and mixtures thereof.

FIELD OF THE INVENTION

This invention relates generally to the cosmetics field and, more particularly to new antioxidative preparations, optionally in encapsulated form, to processes for their production and to their use in the cosmetics field and in the field of food supplements.

PRIOR ART

The desire for eternal youth and beauty existed even in ancient times. Whereas legend has it that Cleopatra regularly bathed in asses' milk—today we know about the effect of the proteins present in such milk—less well-off ladies had to hope that their wish would be heard by the gods. It has to be assumed that this was only rarely crowned with success. Nowadays, a youthful appearance and a skin virtually free from wrinkles is not the privilege of just a few, but is basically available to all women despite the occasionally considerable differences in the price of the preparations. Even if cosmetic chemistry cannot work miracles, knowledge of the biochemical processes in the cells of skin and hair has increased enormously in recent years. As a result, there are of course theories as to how damage caused by natural ageing or environmental influences can be prevented or eliminated. However, the demands that female (and increasingly male) consumers expect such anti-ageing preparations to sastisfy have also increased. Quite apart from the fact that, basically, the preparations are expected to have a “caring” character and to show optimal compatibility with the skin and, optionally, the mucosa, they are required to provide protection against UV radiation and environmental toxins and to stimulate the immune system and the skin functions. Of particular importance in this regard are substances which are capable of trapping free radicals and converting them into substances harmless to the metabolism. Although many substances, particularly vitamin E and its derivatives, are already known for this purpose, Accordingly, the problem addressed by the present invention was to provide new antioxidants that would satisfy the complex requirement profile described above. In addition, with the BSE debate in mind, this “multifunction component” would be a vegetable product.

DESCRIPTION OF THE INVENTION

The present invention relates to antioxidative preparations containing

-   -   (a) at least two extracts selected from the group consisting of         Vaccinium myrtillus, Trifolium pratense, Vitis vinifera and Thea         vinensis and     -   (b) vitamin E and/or vitamin C.

It has surprisingly been found that the mixtures according to the invention have a synergistic antioxidative and phytohormonal effect and, when orally and topically applied, lead to vitalization and regeneration of the skin functions, smooth wrinkles, protect the skin against environmental influences and dehydration and, hence, act quite generally as antiageing components. The extracts may of course also be replaced by the enriched active-substance mixtures. Accordingly, the present invention also relates to antioxidative preparations containing

-   -   (a) at least two active components selected from the group         consisting of anthocyanosides, isoflavone glucosides and         polyphenols and     -   (b) tocopherol and/or ascorbic acid.

Irrespective of whether the extracts or the active substances present therein are directly used, the preparations may contain components (a) and

-   -   (b)—based on the solid content—in a ratio by weight of 10:90 to         90:10, preferably 25:75 to 75:25 and more particularly 40:60 to         60:40.         Vaccinium myrtillus

Vaccinium myrtillus, the bilberry or blueberry, belongs to the genus Vaccinium of which there are about 450 different species. The vaccinium extracts contain as active substances a mixture of at least 15 different anthocyanosides such as, for example, delphinidin:

In general, the vaccinium extracts contain 20 to 25% by weight of anthocyanosides, 5 to 10% by weight of tannins and small quantities of various alkaloids (for example myrtin and epimyrtin), phenolic acids and glycosides containing quercitrin, isoquercitrin and hyperoside.

Trifolium pratense

Trifolium pratense, also known as “red clover”, is a biennial weed with red to purple-colored flowers which grows to about 80 cm and is at home in Europe and North America. The active substances mainly present are isoflavones and their glucosides such as, for example, daizidin, genistin, ononin and sissotrin:

Isoflavone glucosides R₁ R₂ R₃ R₄ Daizidin H H Glucose H Genistin H H Glucose OH Ononin H CH₃ Glucose H Sissotrin H CH₃ Glucose OH Vitis vinifera

Vitis vinifera, of which the roots can grow to a length of 35 meters, belongs to the family of Vitaceae which are native to Asia and Europe. The active substances present are, above all, polyphenols, such as for example catechol and epicatechol in the seeds:

Thea vinensis

Thea vinensis belongs to the group of tea plants which also includes Thea assam for example. In the context of the present invention, the Thea vinensis extracts are extracts of green, i.e. unfermented tea, which still has a high level of tannins. As with Vitis vinifera, the active substances present—besides caffeine—are polyphenols, such as for example flavonoids, flavonols and catechols, particularly epigallocatechol gallate.

In a preferred embodiment of the invention, the preparations contain as component (a) ternary mixtures of (a1) Vaccinium myrtillus, (a2) Trifolium pratense and either (a3a) Vitis vinifera or (a3b) Thea vinensis. The ratio by weight between the three components (a1):(a2):(a3)—again based on the solids content of the extracts—is 80 to 33:10 to 33:10:34.

Extraction

The extracts may be prepared by methods known per se, i.e. for example by aqueous, alcoholic or aqueous/alcoholic extraction of the plants or parts thereof or the leaves or fruit. Particulars of suitable conventional extraction processes, such as maceration, remaceration, digestion, agitation maceration, vortex extraction, ultrasonic extraction, countercurrent extraction, percolation, repercolation, evacolation (extraction under reduced pressure), diacolation and solid/liquid extraction under continuous reflux in a Soxhlet extractor, which are familiar to the expert and which may all be used in principle, can be found, for example, in Hagers Handbuch der pharmazeutischen Praxis (5th Edition, Vol. 2, pp. 1026-1030, Springer Verlag, Berlin-Heidelberg-New York 1991). Percolation is advantageous for industrial use. Fresh plants or parts thereof are suitable as the starting material although dried plants and/or plant parts which may be mechanically size-reduced before extraction are normally used. Any size reduction methods known to the expert, for example freeze grinding, may be used. Preferred solvents for the extraction process are organic solvents, water (preferably hot water with a temperature above 80° C. and more particularly above 95° C.) or mixtures of organic solvents and water, more particularly low molecular weight alcohols with more or less high water contents. Extraction with methanol, ethanol, pentane, hexane, heptane, acetone, propylene glycols, polyethylene glycols, ethyl acetate and mixtures and water-containing mixtures thereof thereof is particularly preferred. The extraction process is generally carried out at 20 to 100° C., preferably at 30 to 90° C. and more particularly at 60 to 80° C. In one preferred embodiment, the extraction process is carried out in an inert gas atmosphere to avoid oxidation of the ingredients of the extract. This is particularly important where extraction is carried out at temperatures above 40° C. The extraction times are selected by the expert in dependence upon the starting material, the extraction process, the extraction temperature and the ratio of solvent to raw material, etc. After the extraction process, the crude extracts obtained may optionally be subjected to other typical steps, such as for example purification, concentration and/or decoloration. If desired, the extracts thus prepared may be subjected, for example, to the selective removal of individual unwanted ingredients. The extraction process may be carried out to any degree, but is usually continued to exhaustion. Typical yields (=extract dry matter, based on the quantity of raw material used) in the extraction of dried leaves are in the range from 3 to 15 and more particularly 6 to 10% by weight. The present invention includes the observation that the extraction conditions and the yields of the final extracts may be selected according to the desired application. These extracts, which generally have active substance contents (=solids contents) of 0.5 to 10% by weight, may be used as such, although the solvent may also be completely removed by drying, more particularly by spray or freeze drying, a deep red colored solid remaining behind. The extracts may also be used as starting materials for producing the pure active substances mentioned above unless they can be synthesized by a more simple and inexpensive method. Accordingly, the active substance content in the extracts may be from 5 to 100% by weight and is preferably from 50 to 95% by weight. The extracts themselves may be present as water-containing preparations and/or as preparations dissolved in organic solvents and as spray-dried or freeze-dried water-free solids. Suitable organic solvents in this connection are, for example, aliphatic alcohols containing 1 to 6 carbon atoms (for example ethanol), ketones (for example acetone), halogenated hydrocarbons (for example chloroform or methylene chloride), lower esters or polyols (for example glycerol or glycols).

Vitamins

Chemically regarded, vitamins E and C are, on the one hand, tocopherol or a mixture of naturally occurring tocopherols and tocotrienols and derivatives thereof, including the esterification products produced therefrom (for example tocopherol palmitate) and, on the other hand, ascorbic acid. The ratio by weight between the two substances is not critical and may be 10:90 to 90:10, but is preferably 25:75 to 75:25 and more particularly 40:60 to 60:40. The mixture preferably contains at least vitamin E because it contributes towards stabilizing vitamin C in the formulation.

Microcapsules

The preparations according to the invention may be topically applied although they are preferably orally applied. In either case, it has proved to be useful to encapsulate the preparations. In the case of direct application to the skin, the active substance is released by mechanical action on the membrane during application; in the case of oral application, the active component is released with delay either through the pores of the membrane or by gradual dissolution of the membrane.

“Microcapsules” are understood by the expert to be spherical aggregates with a diameter of about 0.1 to about 5 mm which contain at least one solid or liquid core surrounded by at least one continuous membrane. More precisely, they are finely dispersed liquid or solid phases coated with film-forming polymers, in the production of which the polymers are deposited onto the material to be encapsulated after emulsification and coacervation or interfacial polymerization. In another process, molten waxes are absorbed in a matrix (“microsponge”) which, as microparticles, may be additionally coated with film-forming polymers. The microscopically small capsules, also known as nanocapsules, can be dried in the same way as powders. Besides single-core microcapsules, there are also multiple-core aggregates, also known as microspheres, which contain two or more cores distributed in the continuous membrane material. In addition, single-core or multiple-core microcapsules may be surrounded by an additional second, third etc. membrane. The membrane may consist of natural, semisynthetic or synthetic materials. Natural membrane materials are, for example, gum arabic, agar agar, agarose, maltodextrins, alginic acid and salts thereof, for example sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac, polysaccharides, such as starch or dextran, polypeptides, protein hydrolyzates, sucrose and waxes. Semisynthetic membrane materials are inter alia chemically modified celluloses, more particularly cellulose esters and ethers, for example cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and carboxymethyl cellulose, and starch derivatives, more particularly starch ethers and esters. Synthetic membrane materials are, for example, polymers, such as polyacrylates, polyamides, polyvinyl alcohol or polyvinyl pyrrolidone.

Examples of known microcapsules are the following commercial products (the membrane material is shown in brackets) Hallcrest Microcapsules (gelatin, gum arabic), Coletica Thalaspheres (maritime collagen), Lipotec Millicapseln (alginic acid, agar agar), Induchem Unispheres (lactose, microcrystalline cellulose, hydroxypropylmethyl cellulose), Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropylmethyl cellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified agar agar), Kuhs Probiol Nanospheres (phospholipids), Primaspheres and Primasponges (chitosan, alginates) and Primasys (phospholipids).

Reference is also made in this connection to German patent application DE 19712978 A1 (Henkel) which describes chitosan microspheres obtained by mixing chitosans or chitosan derivatives with oil components and introducing the resulting mixtures into alkalized surfactant solutions. In addition, the use of chitosan as an encapsulating material for tocopherol is known from German patent application DE 19756452 A1 (Henkel). Chitosan microcapsules and processes for their production are the subject of earlier patent applications filed by applicants [WO 01/01926, WO 01/01927, WO 01/01928, WO 01/01929].

The scope of protection of the present invention also encompasses encapsulated preparations, especially microcapsules with mean diameters of 0.1 to 5 mm, which consist of a membrane and a matrix containing the active components and which may be obtained, for example, by

-   -   (i) preparing a matrix from gel formers, chitosans and         components (a) and (b),     -   (ii) optionally dispersing the matrix in an oil phase and     -   (iii) treating the dispersed matrix with aqueous solutions of         anionic polymers and optionally removing the oil phase in the         process.

An alternative embodiment are microcapsules with mean diameters of 0.1 to 5 mm which consist of a membrane and a matrix containing the active components and which may be obtained, for example, by

-   -   (i) preparing a matrix from gel formers, anionic polymers and         active components (a) and (b),     -   (ii) optionally dispersing the matrix in an oil phase and     -   (iii) treating the dispersed matrix with aqueous chitosan         solutions and optionally removing the oil phase in the process.

The microcapsules according to the invention have the particular advantage that they are highly stable to surfactants and, hence, can also be stably incorporated in cosmetic preparations without being dissolved during storage. In the case of oral application, the advantage lies in high mucous membrane compatibility coupled with complete toxicological harmlessness.

Other embodiments of the present invention are two processes for the production of microcapsules with mean diameters of 0.1 to 5 mm consisting of a membrane and a matrix containing the active components, in which either

-   -   (i) a matrix is prepared from gel formers, chitosans and         components (a) and (b),     -   (ii) the matrix is optionally dispersed in an oil phase and     -   (iii) the dispersed matrix is treated with aqueous solutions of         anionic polymers and the oil phase is optionally removed in the         process; or     -   (i) a matrix is prepared from gel formers, anionic polymers and         components (a) and (b),     -   (ii) the matrix is optionally dispersed in an oil phase and     -   (iii) the dispersed matrix is treated with aqueous chitosan         solutions and the oil phase is optionally removed in the         process.         Gel Formers

Preferred gel formers for the purposes of the invention are substances which are capable of forming gels in aqueous solution at temperatures above 40° C. Typical examples of such gel formers are heteropolysaccharides and proteins. Preferred thermogelling heteropoly-saccharides are agaroses which may be present in the form of the agar agar obtainable from red algae, even together with up to 30% by weight of non-gel-forming agaropectins. The principal constituent of agaroses are linear polysaccharides of D-galactose and 3,6-anhydro-L-galactose with alternate β-1,3- and β-1,4-glycosidic bonds. The heteropolysaccharides preferably have a molecular weight of 110,000 to 160,000 and are both odorless and tasteless. Suitable alternatives are pectins, xanthans (including xanthan gum) and mixtures thereof. Other preferred types are those which—in 1% by weight aqueous solution—still form gels that do not melt below 80° C. and solidify again above 40° C. Examples from the group of thermogelling proteins are the various gelatins.

Chitosans

Chitosans are biopolymers which belong to the group of hydrocolloids. Chemically, they are partly deacetylated chitins differing in their molecular weights which contain the following—idealized—monomer unit:

In contrast to most hydrocolloids, which are negatively charged at biological pH values, chitosans are cationic biopolymers under these conditions. The positively charged chitosans are capable of interacting with oppositely charged surfaces and are therefore used in cosmetic hair-care and body-care products and pharmaceutical preparations (cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A6, Weinheim, Verlag Chemie, 1986, pages 231-332). Overviews of this subject have also been published, for example, by B. Gesslein et al. in HAPPI 27, 57 (1990), O. Skaugrud in Drug Cosm. Ind. 148, 24 (1991) and E. Onsoyen et al. in Seifen-Öle-Fette-Wachse 117, 633 (1991). Chitosans are produced from chitin, preferably from the shell residues of crustaceans which are available in large quantities as inexpensive raw materials. In a process described for the first time by Hackmann et al., the chitin is normally first deproteinized by addition of bases, demineralized by addition of mineral acids and, finally, deacetylated by addition of strong bases, the molecular weights being distributed over a broad spectrum. Corresponding processes are known, for example, from Makromol. Chem. 177, 3589 (1976) or French patent application FR 2701266 A. Preferred types are those which are disclosed in German patent applications DE 4442987 A1 and DE 19537001 A1 (Henkel) and which have an average molecular weight of 10,000 to 500,000 dalton or 800,000 to 1,200,000 dalton and/or a Brookfield viscosity (1% by weight in glycolic acid) below 5,000 mPas, a degree of deacetylation of 80 to 88% and an ash content of less than 0.3% by weight. In the interests of better solubility in water, the chitosans are generally used in the form of their salts, preferably as glycolates.

Oil Phase

Before formation of the membrane, the matrix may optionally be dispersed in an oil phase. Suitable oils for this purpose are, for example, Guerbet alcohols based on fatty alcohols containing 6 to 18 and preferably 8 to 10 carbon atoms, esters of linear C₆₋₂₂ fatty acids with linear C₆₋₂₂ fatty alcohols, esters of branched C₆₋₁₃ carboxylic acids with linear C₆₋₂₂ fatty alcohols such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. Also suitable are esters of linear C₆₋₂₂ fatty acids with branched alcohols, more particularly 2-ethyl hexanol, esters of hydroxycarboxylic acids with linear or branched C₆₋₂₂ fatty alcohols, more especially Dioctyl Malate, esters of linear and/or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols, triglycerides based on C₆₋₁₀ fatty acids, liquid mono-/di-/triglyceride mixtures based on C₆₋₁₈ fatty acids, esters of C₆₋₂₂ fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, more particularly benzoic acid, esters of C₂₋₁₂ dicarboxylic acids with linear or branched alcohols containing 1 to 22 carbon atoms or polyols containing 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C₆₋₂₂ fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and/or branched C₆₋₂₂ alcohols (for example Finsolv® TN), linear or branched, symmetrical or nonsymmetrical dialkyl ethers containing 6 to 22 carbon atoms per alkyl group, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and/or aliphatic or naphthenic hydrocarbons, for example squalane, squalene or dialkyl cyclohexanes.

Anionic Polymers

The function of the anionic polymers is to form membranes with the chitosans. Preferred anionic polymers are salts of alginic acid. The alginic acid is a mixture of carboxyl-containing polysaccharides with the following idealized monomer unit:

The average molecular weight of the alginic acid or the alginates is in the range from 150,000 to 250,000. Salts of alginic acid and complete and partial neutralization products thereof are understood in particular to be the alkali metal salts, preferably sodium alginate (“algin”), and the ammonium and alkaline earth metal salts. Mixed alginates, for example sodium/magnesium or sodium/calcium alginates, are particularly preferred. In an alternative embodiment of the invention, however, anionic chitosan derivatives, for example the carboxylation and above all succinylation products described, for example, in German patent DE 3713099 C2 (L'Oreal) and German patent application DE 19604180 A1 (Henkel) are also suitable for this purpose. Alternatively, poly(meth)acrylates with average molecular weights of 5,000 to 50,000 dalton and the various carboxymethyl celluloses may also be used. Instead of the anionic polymers, anionic surfactants or low molecular weight inorganic salts, such as pyrophosphates for example, may also be used for forming the membrane. Production of Microcapsules

To produce the microcapsules, a 1 to 10 and preferably 2 to 5% by weight aqueous solution of the gel former, preferably agar agar, is normally prepared and heated under reflux. A second aqueous solution containing the chitosan in quantities of 0.1 to 2 and preferably 0.25 to 0.5% by weight and the active substance (componemts a and b) in quantities of 0.1 to 25 and preferably 0.25 to 10% by weight is added in the boiling heat, preferably at 80 to 100° C.; this mixture is called the matrix. Accordingly, the charging of the microcapsules with active substances may also comprise 0.1 to 25% by weight, based on the weight of the capsules. If desired, water-insoluble constituents, for example inorganic pigments, may be added at this stage to adjust viscosity, generally in the form of aqueous or aqueous/alcoholic dispersions. In addition, to emulsify or disperse the active substances, it can be useful to add emulsifiers and/or solubilizers to the matrix. After its preparation from gel former, chitosan and active substances (components a and b), the matrix may optionally be very finely dispersed in an oil phase with intensive shearing in order to produce small particles in the subsequent encapsulation process. It has proved to be particularly advantageous in this regard to heat the matrix to temperatures in the range from 40 to 60° C. while the oil phase is cooled to 10 to 20° C. The actual encapsulation, i.e. formation of the membrane by contacting the chitosan in the matrix with the anionic polymers, takes place in the last, again compulsory step. To this end, it is advisable to wash the matrix optionally dispersed in the oil phase with an aqueous ca. 1 to 50 and preferably 10 to 15% by weight aqueous solution of the anionic polymer and, if necessary, to remove the oil phase either at the same time or afterwards. The resulting aqueous preparations generally have a microcapsule content of 1 to 10% by weight. In some cases, it can be of advantage for the solution of the polymers to contain other ingredients, for example emulsifiers or preservatives. After filtration, microcapsules with a mean diameter of preferably about 1 mm are obtained. It is advisable to sieve the capsules to ensure a uniform size distribution. The microcapsules thus obtained may have any shape within production-related limits, but are preferably substantially spherical. Alternatively, the anionic polymers may also be used for the preparation of the matrix and encapsulation may be carried out with the chitosans.

Pro-Liposomes

Instead of the described microcapsules, pro-liposomes may also be used as carriers for the active-substance mixtures. By way of explanation, it is pointed out that pro-liposomes contain no water and only take up water to form true liposomes when they are introduced into a watery environment. Accordingly, the present invention also relates to pro-liposome-encapsulated antioxidant mixtures which contain components (a) and (b) and which are obtained by treating the mixtures with lecithins and/or phospholipids in cosmetically acceptable solvents.

Lecithins are known among experts as glycerophospholipids which are formed from fatty acids, glycerol, phosphoric acid and choline by esterification. Accordingly, lecithins are also frequently referred to by experts as phosphatidyl cholines (PCs).

Lecithin is schematized in the above formula, where R typically represents linear aliphatic hydrocarbon radicals containing 15 to 17 carbon atoms and up to 4 cis-double bonds. Examples of natural lecithins suitable for encapsulation are the kephalins which are also known as phosphatidic acids and which are derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids. By contrast, phospholipids are generally understood to be mono- and preferably diesters of phosphoric acid with glycerol (glycero-phosphates) which are normally classed as fats. Sphingosines and sphingolipids are also suitable for liposomal encapsulation. The use of lecithins or phospholipids for the production of liposomes is described, for example, by M. Schneider in Fat Sci. Technol. 94, 524 (1992) and by U. Citernesi et al. in Cosm. Toil. 110, 57 (1995). Reference is also made in this connection to European patent EP 0525188 B1 (Takeda) which desribes liposomes of which the membrane consists of surfactants and lecithins. Production of Pro-Liposomes

The present invention also relates to a process for the production of pro-liposome-encapsulated antioxidant mixtures which contain components (a) and (b) and which are obtained by treating the mixtures with lecithins and/or phospholipids in cosmetically acceptable solvents. To this end, either the active-substance mixtures are normally introduced first in a solvent and contacted with the lecithins or phospholipids at temperatures of 30 to 70° C. or the water-free mixtures are stirred into a solution of the lecithins or phospholipids. The active substances and the lecithins and/or phospholipids may be used in a ratio by weight of 1:20 to 5:1 and are preferably used in a ratio by weight of 1:2 to 4:1. Preferred solvents are lower alcohols containing 1 to 4 carbon atoms, for example ethanol or polyols, which generally contain 2 to 15 carbon atoms and at least two hydroxyl groups. Propylene glycol is preferred.

Commercial Applications

Both the preparations according to the invention based on (a) the extracts or the active substances isolated therefrom and (b) the vitamins E and/or C and the microcapsules produced with them have excellent antioxidative properties. Accordingly, the present invention also relates to the use of the optionally encapsulated active-substance mixtures as antioxidants, as anti-ageing components, for the production of cosmetic and/or pharmaceutical preparations and as food supplements or animal feed additives. The mixtures may be identical with the preparations or may contain them in quantities of 0.1 to 50, preferably 1 to 30 and more particularly 5 to 15% by weight. For this use, the preparations may be preparations for both topical and oral application, oral application being particularly preferred for the encapsulated preparations.

Cosmetic and/or Pharmaceutical Preparations

Where the antioxidant mixtures according to the invention—encapsulated or not—are used for the production of cosmetic or pharmaceutical preparations, the preparations are normally formulated as creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compounds, stick preparations, powders or ointments. These preparations may also contain mild surfactants, oil components, emulsifiers, pearlizing waxes, consistency factors, thickeners, superfatting agents, stabilizers, polymers, silicone compounds, fats, waxes, lecithins, phospholipids, biogenic agents, UV protection factors, antioxidants, deodorants, antiperspirants, antidandruff agents, film formers, swelling agents, insect repellents, self-tanning agents, tyrosine inhibitors (depigmenting agents), hydrotropes, solubilizers, perservatives, perfume oils, dyes and the like as further auxiliaries and additives.

Surfactants

Suitable surfactants are anionic, nonionic, cationic and/or amphoteric or zwitterionic surfactants which may be present in the preparations in quantities of normally about 1 to 70% by weight, preferably 5 to 50% by weight and more preferably 10 to 30% by weight. Typical examples of anionic surfactants are soaps, alkyl benzenesulfonates, alkanesulfonates, olefin sulfonates, alkylether sulfonates, glycerol ether sul- fonates, α-methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and salts thereof, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as, for example, acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (particularly wheat-based vegetable products) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they may have a conventional homolog distribution although they preferably have a narrow-range homolog distribution. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers and mixed formals, optionally partly oxidized alk(en)yl oligoglycosides or glucuronic acid derivatives, fatty acid-N-alkyl glucamides, protein hydrolyzates (particularly wheat-based vegetable products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they may have a conventional homolog distribution, although they preferably have a narrow-range homolog distribution. Typical examples of cationic surfactants are quaternary ammonium compounds, for example dimethyl distearyl ammonium chloride, and esterquats, more particularly quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are all known compounds. Information on their structure and production can be found in relevant synoptic works, cf. for example J. Falbe (ed.), “Surfactants in Consumer Products”, Springer Verlag, Berlin, 1987, pages 54 to 124 or J. Falbe (ed.), “Katalysatoren, Tenside und Mineralöladditive (Catalysts, Surfactants and Mineral Oil Additives)”, Thieme Verlag, Stuttgart, 1978, pages 123-217. Typical examples of particularly suitable mild, i.e. particularly dermatologically compatible, surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and/or di-alkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, α-olefin sulfonates, ether carboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines, amphoacetals and/or protein fatty acid condensates, preferably based on wheat proteins.

Oil Components

Suitable oil components are, for example, Guerbet alcohols based on fatty alcohols containing 6 to 18 and preferably 8 to 10 carbon atoms, esters of linear C₆₋₂₂ fatty acids with linear or branched C₆₋₂₂ fatty alcohols or esters of branched C₆₋₁₃ carboxylic acids with linear or branched C₆₋₂₂ fatty alcohols such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. Also suitable are esters of linear C₆₋₂₂ fatty acids with branched alcohols, more particularly 2-ethyl hexanol, esters of C₁₈₋₃₈ alkylhydroxycarboxylic acids with linear or branched C₆₋₂₂ fatty alcohols (cf. DE 197 56 377 A1), more especially Dioctyl Malate, esters of linear and/or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols, triglycerides based on C₆₋₁₀ fatty acids, liquid mono-, di- and triglyceride mixtures based on C₆₋₁₈ fatty acids, esters of C₆₋₂₂ fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, more particularly benzoic acid, esters of C₂₋₁₂ dicarboxylic acids with linear or branched alcohols containing 1 to 22 carbon atoms or polyols containing 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched Cr₂₂ fatty alcohol carbonates, such as Dicaprylyl Carbonate (Cetiol® CC) for example, Guerbet carbonates based on C₆₋₁₈ and preferably C₈₋₁₀ fatty alcohols, esters of benzoic acid with linear and/or branched C₈₋₂₂ alcohols (for example Finsolv® TN), linear or branched, symmetrical or nonsymmetrical dialkyl ethers containing 6 to 22 carbon atoms per alkyl group, such as Dicaprylyl Ether (Cetiol® OE) for example, ring opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicone, silicon methicone types, etc.) and/or aliphatic or naphthenic hydrocarbons such as, for example, squalane, squalene or dialkyl cyclohexanes.

Emulsifiers

Suitable emulsifiers are, for example, nonionic surfactants from at least one of the following groups:

-   -   products of the addition of 2 to 30 mol ethylene oxide and/or 0         to 5 mol propylene oxide onto linear C₈₋₂₂ fatty alcohols, onto         C₁₂₋₂₂ fatty acids, onto alkyl phenols containing 8 to 15 carbon         atoms in the alkyl group and onto alkylamines containing 8 to 22         carbon atoms in the alkyl group;     -   alkyl and/or alkenyl oligoglycosides containing 8 to 22 carbon         atoms in the alk(en)yl group and ethoxylated analogs thereof;     -   addition products of 1 to 15 mol ethylene oxide onto castor oil         and/or hydrogenated castor oil;     -   addition products of 15 to 60 mol ethylene oxide onto castor oil         and/or hydrogenated castor oil;     -   partial esters of glycerol and/or sorbitan with unsaturated,         linear or saturated, branched fatty acids containing 12 to 22         carbon atoms and/or hydroxycarboxylic acids containing 3 to 18         carbon atoms and addition products thereof onto 1 to 30 mol         ethylene oxide;     -   partial esters of polyglycerol (average degree of         self-condensation 2 to 8), polyethylene glycol (molecular weight         400 to 5,000), trimethylolpropane, pentaerythritol, sugar         alcohols (for example sorbitol), alkyl glucosides (for example         methyl glucoside, butyl glucoside, lauryl glucoside) and         polyglucosides (for example cellulose) with saturated and/or         unsaturated, linear or branched fatty acids containing 12 to 22         carbon atoms and/or hydroxycarboxylic acids containing 3 to 18         carbon atoms and addition products thereof onto 1 to 30 mol         ethylene oxide;     -   mixed esters of pentaerythritol, fatty acids, citric acid and         fatty alcohol according to DE 1165574 PS and/or mixed esters of         fatty acids containing 6 to 22 carbon atoms, methyl glucose and         polyols, preferably glycerol or polyglycerol,     -   mono-, di- and trialkyl phosphates and mono-, di- and/or         tri-PEG-alkyl phosphates and salts thereof,     -   wool wax alcohols,     -   polysiloxane/polyalkyl/polyether copolymers and corresponding         derivatives,     -   block copolymers, for example Polyethyleneglycol-30         Dipolyhydroxystearate;     -   polymer emulsifiers, for example Pemulen types (TR-1, TR-2) of         Goodrich;     -   polyalkylene glycols and     -   glycerol carbonate.

Ethylene Oxide Addition Products

The addition products of ethylene oxide and/or propylene oxide onto fatty alcohols, fatty acids, alkylphenols or onto castor oil are known commercially available products. They are homolog mixtures of which the average degree of alkoxylation corresponds to the ratio between the quantities of ethylene oxide and/or propylene oxide and substrate with which the addition reaction is carried out. C₁₂₋₁₈ fatty acid monoesters and diesters of addition products of ethylene oxide onto glycerol are known as lipid layer enhancers for cosmetic formulations from DE 2024051 PS.

Alkyl and/or Alkenyl Oligoglycosides

Alkyl and/or alkenyl oligoglycosides, their production and their use are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols containing 8 to 18 carbon atoms. So far as the glycoside unit is concerned, both monoglycosides in which a cyclic sugar unit is attached to the fatty alcohol by a glycoside bond and oligomeric glycosides with a degree of oligomerization of preferably up to about 8 are suitable. The degree of oligomerization is a statistical mean value on which the homolog distribution typical of such technical products is based.

Partial Glycerides

Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, hydroxystearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride, oleic acid monoglyceride, oleic acid diglyceride, ricinoleic acid monoglyceride, ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic acid diglyceride, linolenic acid monoglyceride, linolenic acid diglyceride, erucic acid monoglyceride, erucic acid diglyceride, tartaric acid monoglyceride, tartaric acid diglyceride, citric acid monoglyceride, citric acid diglyceride, malic acid monoglyceride, malic acid diglyceride and technical mixtures thereof which may still contain small quantities of triglyceride from the production process. Addition products of 1 to 30 and preferably 5 to 10 mol ethylene oxide onto the partial glycerides mentioned are also suitable.

Sorbitan Esters

Suitable sorbitan esters are sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitan dierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitan sesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate and technical mixtures thereof. Addition products of 1 to 30 and preferably 5 to 10 mol ethylene oxide onto the sorbitan esters mentioned are also suitable.

Polyglycerol Esters

Typical examples of suitable polyglycerol esters are Polyglyceryl-2 Dipolyhydroxystearate (Dehymuls® PGPH), Polyglycerin-3-Diisostearate (Lameform® TGI), Polyglyceryl-4 Isostearate (Isolan® GI 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate (Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010/90), Polyglyceryl-3 Cetyl Ether (Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403), Polyglyceryl Dimerate Isostearate and mixtures thereof. Examples of other suitable polyolesters are the mono-, di- and triesters of trimethylolpropane or pentaerythritol with lauric acid, cocofatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like optionally reacted with 1 to 30 mol ethylene oxide.

Anionic Emulsifiers

Typical anionic emulsifiers are aliphatic fatty acids containing 12 to 22 carbon atoms such as, for example, palmitic acid, stearic acid or behenic acid and dicarboxylic acids containing 12 to 22 carbon atoms such as, for example, azelaic acid or sebacic acid.

Amphoteric and Cationic Emulsifiers

Other suitable emulsifiers are zwitterionic surfactants. Zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example cocoacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. Ampholytic surfactants are also suitable emulsifiers. Ampholytic surfactants are surface-active compounds which, in addition to a C_(8/18) alkyl or acyl group, contain at least one free amino group and at least one —COOH— or —SO₃H— group in the molecule and which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coco-alkylaminopropionate, cocoacylaminoethyl aminopropionate and C_(12/18) acyl sarcosine. Finally, cationic surfactants are also suitable emulsifiers, those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.

Fats and Waxes

Typical examples of fats are glycerides, i.e. solid or liquid, vegetable or animal products which consist essentially of mixed glycerol esters of higher fatty acids. Suitable waxes are inter alia natural waxes such as, for example, candelilla wax, carnauba wax, Japan wax, espartograss wax, cork wax, guaruma wax, rice oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax), uropygial fat, ceresine, ozocerite (earth wax), petrolatum, paraffin waxes and microwaxes; chemically modified waxes (hard waxes) such as, for example, montan ester waxes, sasol waxes, hydrogenated jojoba waxes and synthetic waxes such as, for example, polyalkylene waxes and polyethylene glycol waxes. Besides the fats, other suitable additives are fat-like substances, such as lecithins and phospholipids. Lecithins are known among experts as glycerophospholipids which are formed from fatty acids, glycerol, phosphoric acid and choline by esterification. Accordingly, lecithins are also frequently referred to by experts as phosphatidyl cholines (PCs). Examples of natural lecithins are the kephalins which are also known as phosphatidic acids and which are derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids. By contrast, phospholipids are generally understood to be mono- and preferably diesters of phosphoric acid with glycerol (glycerophosphates) which are normally classed as fats. Sphingosines and sphingolipids are also suitable.

Pearlizing Waxes

Suitable pearlizing waxes are, for example, alkylene glycol esters, especially ethylene glycol distearate; fatty acid alkanolamides, especially cocofatty acid diethanolamide; partial glycerides, especially stearic acid monoglyceride; esters of polybasic, optionally hydroxysubstituted carboxylic acids with fatty alcohols containing 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; fatty compounds, such as for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates which contain in all at least 24 carbon atoms, especially laurone and distearylether; fatty acids, such as stearic acid, hydroxystearic acid or behenic acid, ring opening products of olefin epoxides containing 12 to 22 carbon atoms with fatty alcohols containing 12 to 22 carbon atoms and/or polyols containing 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.

Consistency Factors and Thickeners

The consistency factors mainly used are fatty alcohols or hydroxyfatty alcohols containing 12 to 22 and preferably 16 to 18 carbon atoms and also partial glycerides, fatty acids or hydroxyfatty acids. A combination of these substances with alkyl oligoglucosides and/or fatty acid N-methyl glucamides of the same chain length and/or polyglycerol poly-12-hydroxystearates is preferably used. Suitable thickeners are, for example, Aerosil® types (hydrophilic silicas), polysaccharides, more especially xanthan gum, guar-guar, agar-agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, also relatively high molecular weight polyethylene glycol monoesters and diesters of fatty acids, polyacrylates (for example Carbopols® and Pemulen types [Goodrich]; Synthalens® [Sigma]; Keltrol types [Kelco]; Sepigel types [Seppic]; Salcare types [Allied Colloids]), polyacrylamides, polymers, polyvinyl alcohol and polyvinyl pyrrolidone. Other consistency factors which have proved to be particularly effective are bentonites, for example Bentone® Gel VS-5PC (Rheox) which is a mixture of cyclopentasiloxane, Disteardimonium Hectorite and propylene carbonate. Other suitable consistency factors are surfactants such as, for example, ethoxylated fatty acid glycerides, esters of fatty acids with polyols, for example pentaerythritol or trimethylol propane, narrow-range fatty alcohol ethoxylates or alkyl oligoglucosides and electrolytes, such as sodium chloride and ammonium chloride.

Superfatting Agents

Superfatting agents may be selected from such substances as, for example, lanolin and lecithin and also polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the fatty acid alkanolamides also serving as foam stabilizers.

Stabilizers

Metal salts of fatty acids such as, for example, magnesium, aluminium and/or zinc stearate or ricinoleate may be used as stabilizers.

Polymers

Suitable cationic polymers are, for example, cationic cellulose derivatives such as, for example, the quaternized hydroxyethyl cellulose obtainable from Amerchol under the name of Polymer JR 400®, cationic starch, copolymers of diallyl ammonium salts and acrylamides, quaternized vinyl pyrrolidone/vinyl imidazole polymers such as, for example, Luviquat® (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides such as, for example, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen (Lamequat® L, Grünau), quaternized wheat poly- peptides, polyethyleneimine, cationic silicone polymers such as, for example, amodimethicone, copolymers of adipic acid and dimethylamino-hydroxypropyl diethylenetriamine (Cartaretine®, Sandoz), copolymers of acrylic acid with dimethyl diallyl ammonium chloride (Merquat® 550, Chemviron), polyaminopolyamides as described, for example, in FR 2252840 A and crosslinked water-soluble polymers thereof, cationic chitin derivatives such as, for example, quaternized chitosan, optionally in micro-crystalline distribution, condensation products of dihaloalkyls, for example dibromobutane, with bis-dialkylamines, for example bis-dimethylamino-1,3-propane, cationic guar gum such as, for example, Jaguar®CBS, Jaguar®C-17, Jaguar®C-16 of Celanese, quaternized ammonium salt polymers such as, for example, Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 of Miranol.

Suitable anionic, zwitterionic, amphoteric and nonionic polymers are, for example, vinyl acetate/crotonic acid copolymers, vinyl pyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinylether/maleic anhydride copolymers and esters thereof, uncrosslinked and polyol-crosslinked polyacrylic acids, acrylamido-propyl trimethylammonium chloride/acrylate copolymers, octylacryl-amide/methyl methacrylate/tert.-butylaminoethyl methacrylate/2-hydroxy-propyl methacrylate copolymers, polyvinyl pyrrolidone, vinyl pyrrolidone/vinyl acetate copolymers, vinyl pyrrolidone/dimethylaminoethyl methacrylate/vinyl caprolactam terpolymers and optionally derivatized cellulose ethers and silicones. Other suitable polymers and thickeners can be found in Cosm. Toil., 108, 95 (1993).

Silicone Compounds

Suitable silicone compounds are, for example, dimethyl polysiloxanes, methylphenyl polysiloxanes, cyclic silicones and amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone compounds which may be both liquid and resin-like at room temperature. Other suitable silicone compounds are simethicones which are mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates. A detailed overview of suitable volatile silicones can be found in Todd et al. in Cosm. Toil. 91, 27 (1976).

UV Protection Factors and Antioxidants

UV protection factors in the context of the invention are, for example, organic substances (light filters) which are liquid or crystalline at room temperature and which are capable of absorbing ultraviolet radiation and of releasing the energy absorbed in the form of longer-wave radiation, for example heat. UV-B filters can be oil-soluble or water-soluble. The following are examples of oil-soluble substances:

-   -   3-benzylidene camphor or 3-benzylidene norcamphor and         derivatives thereof, for example 3-(4-methylbenzylidene)-camphor         as described in EP 0693471 B1;     -   4-aminobenzoic acid derivatives, preferably         4-(dimethylamino)-benzoic acid-2-ethylhexyl ester,         4-(dimethylamino)-benzoic acid-2-octyl ester and         4-(dimethylamino)-benzoic acid amyl ester;     -   esters of cinnamic acid, preferably 4-methoxycinnamic         acid-2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester,         4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic         acid-2-ethylhexyl ester (Octocrylene);     -   esters of salicylic acid, preferably salicylic acid-2-ethylhexyl         ester, salicylic acid4-isopropylbenzyl ester, salicylic acid         homomenthyl ester;     -   derivatives of benzophenone, preferably         2-hydroxy-4-methoxybenzo-phenone,         2-hydroxy-4-methoxy4′-methylbenzophenone,         2,2′-dihydroxy-4-methoxybenzophenone;     -   esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic         acid di-2-ethylhexyl ester;     -   triazine derivatives such as, for example,         2,4,6-trianilino-(p-carbo-2′-ethyl-1′-hexyloxy)-1,3,5-triazine         and Octyl Triazone as described in EP 0818450 Alor Dioctyl         Butamido Triazone (Uvasorb® HEB);     -   propane-1,3-diones such as, for example,         1-(4-tert.butylphenyl)-3-(4′-methoxyphenyl)-propane-1,3-dione;     -   ketotricyclo(5.2.1.0)decane derivatives as described in EP         0694521 B1.

Suitable water-soluble substances are

-   -   2-phenylbenzimidazole-5-sulfonic acid and alkali metal, alkaline         earth metal, ammonium, alkylammonium, alkanolammonium and         glucammonium salts thereof;     -   sulfonic acid derivatives of benzophenones, preferably         2-hydroxy4-methoxybenzophenone-5-sulfonic acid and salts         thereof;     -   sulfonic acid derivatives of 3-benzylidene camphor such as, for         example, 4-(2-oxo-3-bornylidenemethyl)-benzene sulfonic acid and         2-methly-5-(2-oxo-3-bornylidene)-sulfonic acid and salts         thereof.

Typical UV-A filters are, in particular, derivatives of benzoyl methane such as, for example, 1-(4′-tert.butylphenyl)-3-(4′-methoxyphenyl)-propane-1,3-dione, 4-tert.butyl-4′-methoxydibenzoyl methane (Parsol® 1789) or 1-phenyl-3-(4′-isopropylphenyl)-propane-1,3-dione and the enamine compounds described in DE 19712033 A1 (BASF). The UV-A and UV-B filters may of course also be used in the form of mixtures. Particularly favorable combinations consist of the derivatives of benzoyl methane, for example 4-tert.butyl-4′-methoxydibenzoylmethane (Parsol® 1789) and 2-cyano-3,3-phenylcinnamic acid-2-ethyl hexyl ester (Octocrylene) in combination with esters of cinnamic acid, preferably 4-methoxycinnamic acid-2-ethyl hexyl ester and/or 4-methoxycinnamic acid propyl ester and/or 4-methoxycinnamic acid isoamyl ester. Combinations such as these are advantageously combined with water-soluble filters such as, for example, 2-phenylbenzimidazole-5-sulfonic acid and alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts thereof.

Besides the soluble substances mentioned, insoluble light-blocking pigments, i.e. finely dispersed metal oxides or salts, may also be used for this purpose. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide and also oxides of iron, zirconium oxide, silicon, manganese, aluminium and cerium and mixtures thereof. Silicates (talcum), barium sulfate and zinc stearate may be used as salts. The oxides and salts are used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have a mean diameter of less than 100 nm, preferably between 5 and 50 nm and more preferably between 15 and 30 nm. They may be spherical in shape although ellipsoidal particles or other non-spherical particles may also be used. The pigments may also be surface-treated, i.e. hydrophilicized or hydrophobicized. Typical examples are coated titanium dioxides, for example Titandioxid T 805 (Degussa) and Eusolex® T2000 (Merck). Suitable hydrophobic coating materials are, above all, silicones and, among these, especially trialkoxyoctylsilanes or simethicones. So-called micro- or nanopigments are preferably used in sun protection products. Micronized zinc oxide is preferably used. Other suitable UV filters can be found in P. Finkel's review in SÖFW-Journal 122, 543 (1996) and in Parf. Kosm. 3, 11 (1999).

Besides the two groups of primary sun protection factors mentioned above, secondary sun protection factors of the antioxidant type may also be used. Secondary sun protection factors of the antioxidant type interrupt the photochemical reaction chain which is initiated when UV rays penetrate into the skin. Typical examples are amino acids (for example glycine, histidine, tyrosine, tryptophane) and derivatives thereof, imidazoles (for example urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (for example anserine), carotinoids, carotenes (for example α-carotene, β-carotene, lycopene) and derivatives thereof, chlorogenic acid and derivatives thereof, liponic acid and derivatives thereof (for example dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (for example thioredoxine, glutathione, cysteine, cystine, cystamine and glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters thereof) and their salts, dilaurylthiodipropionate, distearylthiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (for example butionine sulfoximines, homocysteine sulfoximine, butionine sulfones, penta-, hexa- and hepta-thionine sulfoximine) in very small compatible dosages (for example pmole to μmole/kg), also (metal) chelators (for example α-hydroxyfatty acids, palmitic acid, phytic acid, lactoferrine), α-hydroxy acids (for example citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (for example γ-linolenic acid, linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C and derivatives thereof (for example ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (for example vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, α-glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butyl hydroxyanisole, nordihydroguaiac resin acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, Superoxid-Dismutase, zinc and derivatives thereof (for example ZnO, ZnSO₄), selenium and derivatives thereof (for example selenium methionine), stilbenes and derivatives thereof (for example stilbene oxide, trans-stilbene oxide) and derivatives of these active substances suitable for the purposes of the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids).

Biogenic Agents

In the context of the invention, biogenic agents are, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, (deoxy)ribonucleic acid and fragmentation products thereof, β-glucans, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts, for example prunus extract, bambara nut extract, and vitamin complexes.

Deodorants and Germ Inhibitors

Cosmetic deodorants counteract, mask or eliminate body odors. Body odors are formed through the action of skin bacteria on apocrine perspiration which results in the formation of unpleasant-smelling degradation products. Accordingly, deodorants contain active principles which act as germ inhibitors, enzyme inhibitors, odor absorbers or odor maskers.

Germ Inhibitors

Basically, suitable germ inhibitors are any substances which act against gram-positive bacteria such as, for example, 4-hydroxy-benzoic acid and salts and esters thereof, N-(4-chlorophenyl)-N′-(3,4-dichlorophenyl)-urea, 2,4,4′-trichloro-2′-hydroxydiphenylether (triclosan), 4-chloro-3,5-dimethylphenol, 2,2′-methylene-bis-(6-bromo-4-chlorophenol), 3-methyl-4-(1-methylethyl)-phenol, 2-benzyl-4-chlorophenol, 3-(4-chlorophenoxy)-propane-1,2-diol, 3-iodo-2-propinyl butyl carbamate, chlorhexidine, 3,4,4′-trichlorocarbanilide (TTC), antibacterial perfumes, thymol, thyme oil, eugenol, clove oil, menthol, mint oil, farnesol, phenoxyethanol, glycerol monocaprate, glycerol monocaprylate, glycerol monolaurate (GML), diglycerol monocaprate (DMC), salicylic acid-N-alkylamides such as, for example, salicylic acid-n-octyl amide or salicylic acid-n-decyl amide.

Enzyme Inhibitors

Suitable enzyme inhibitors are, for example, esterase inhibitors. Esterase inhibitors are preferably trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and, in particular, triethyl citrate (Hydagen® CAT). Esterase inhibitors inhibit enzyme activity and thus reduce odor formation.

Other esterase inhibitors are sterol sulfates or phosphates such as, for example, lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and esters thereof, for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester, hydroxycarboxylic acids and esters thereof, for example citric acid, malic acid, tartaric acid or tartaric acid diethyl ester, and zinc glycinate.

Odor Absorbers

Suitable odor absorbers are substances which are capable of absorbing and largely retaining the odor-forming compounds. They reduce the partial pressure of the individual components and thus also reduce the rate at which they spread. An important requirement in this regard is that perfumes must remain unimpaired. Odor absorbers are not active against bacteria. They contain, for example, a complex zinc salt of ricinoleic acid or special perfumes of largely neutral odor known to the expert as “fixateurs” such as, for example, extracts of ladanum or styrax or certain abietic acid derivatives as their principal component. Odor maskers are perfumes or perfume oils which, besides their odor-masking function, impart their particular perfume note to the deodorants. Suitable perfume oils are, for example, mixtures of natural and synthetic fragrances. Natural fragrances include the extracts of blossoms, stems and leaves, fruits, fruit peel, roots, woods, herbs and grasses, needles and branches, resins and balsams. Animal raw materials, for example civet and beaver, may also be used. Typical synthetic perfume compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Examples of perfume compounds of the ester type are benzyl acetate, p-tert.butyl cyclohexylacetate, linalyl acetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Ethers include, for example, benzyl ethyl ether while aldehydes include, for example, the linear alkanals containing 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal. Examples of suitable ketones are the ionones and methyl cedryl ketone. Suitable alcohols are anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons mainly include the terpenes and balsams. However, it is preferred to use mixtures of different perfume compounds which, together, produce an agreeable fragrance. Other suitable perfume oils are essential oils of relatively low volatility which are mostly used as aroma components. Examples are sage oil, camomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime-blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, ladanum oil and lavendin oil. The following are preferably used either individually or in the form of mixtures: bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice, citrus oil, mandarin oil, orange oil, allylamyl glycolate, cyclovertal, lavendin oil, clary oil, β-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat.

Antiperspirants

Antiperspirants reduce perspiration and thus counteract underarm wetness and body odor by influencing the activity of the eccrine sweat glands. Aqueous or water-free antiperspirant formulations typically contain the following ingredients:

-   -   astringent active principles,     -   oil components,     -   nonionic emulsifiers,     -   co-emulsifiers,     -   consistency factors,     -   auxiliaries in the form of, for example, thickeners or         complexing agents and/or     -   non-aqueous solvents such as, for example, ethanol, propylene         glycol and/or glycerol.

Suitable astringent active principles of antiperspirants are, above all, salts of aluminium, zirconium or zinc. Suitable antihydrotic agents of this type are, for example, aluminium chloride, aluminium chlorohydrate, aluminium dichlorohydrate, aluminium sesquichlorohydrate and complex compounds thereof, for example with 1,2-propylene glycol, aluminium hydroxyallantoinate, aluminium chloride tartrate, aluminium zirconium trichlorohydrate, aluminium zirconium tetrachlorohydrate, aluminium zirconium pentachloro- hydrate and complex compounds thereof, for example with amino acids, such as glycine. Oil-soluble and water-soluble auxiliaries typically encountered in antiperspirants may also be present in relatively small amounts. Oil-soluble auxiliaries such as these include, for example,

-   -   inflammation-inhibiting, skin-protecting or pleasant-smelling         essential oils,     -   synthetic skin-protecting agents and/or     -   oil-soluble perfume oils.

Typical water-soluble additives are, for example, preservatives, water-soluble perfumes, pH adjusters, for example buffer mixtures, water-soluble thickeners, for example water-soluble natural or synthetic polymers such as, for example, xanthan gum, hydroxyethyl cellulose, polyvinyl pyrrolidone or high molecular weight polyethylene oxides.

Film Formers

Standard film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinyl pyrrolidone, vinyl pyrrolidone/vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid and salts thereof and similar compounds.

Antidandruff Agents

Suitable antidandruff agents are Pirocton Olamin (1-hydroxy4-methyl-6-(2,4,4-trimethylpentyl)-2-(1H)-pyridinone monoethanolamine salt), Baypival® (Climbazole), Ketoconazol® (4-acetyl-1-{4-[2-(2,4-dichlorophenyl) r-2-(1H-imidazol-1-ylmethyl)-1,3-d ioxylan-c4-yl methoxy-phenyl}-piperazine, ketoconazole, elubiol, selenium disulfide, colloidal sulfur, sulfur polyethylene glycol sorbitan monooleate, sulfur ricinol polyethoxylate, sulfur tar distillate, salicylic acid (or in combination with hexachlorophene), undecylenic acid, monoethanolamide sulfosuccinate Na salt, Lamepon® UD (protein/undecylenic acid condensate), zinc pyrithione, aluminum pyrithione and magnesium pyrithione/dipyrithione magnesium sulfate.

Swelling Agents

Suitable swelling agents for aqueous phases are montmorillonites, clay minerals, Pemulen and alkyl-modified Carbopol types (Goodrich). Other suitable polymers and swelling agents can be found in R. Lochhead's review in Cosm. Toil. 108, 95 (1993).

Insect Repellents

Suitable insect repellents are N,N-diethyl-m-toluamide, pentane-1,2-diol or Ethyl Butylacetylaminopropionate.

Self-Tanning Agents and Depigmenting Agents

A suitable self-tanning agent is dihydroxyacetone. Suitable tyrosine inhibitors which prevent the formation of melanin and are used in depigmenting agents are, for example, arbutin, ferulic acid, koji acid, coumaric acid and ascorbic acid (vitamin C).

Hydrotropes

In addition, hydrotropes, for example ethanol, isopropyl alcohol or polyols, may be used to improve flow behavior. Suitable polyols preferably contain 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols may contain other functional groups, more especially amino groups, or may be modified with nitrogen. Typical examples are

-   -   glycerol;     -   alkylene glycols such as, for example, ethylene glycol,         diethylene glycol, propylene glycol, butylene glycol, hexylene         glycol and polyethylene glycols with an average molecular weight         of 100 to 1000 dalton;     -   technical oligoglycerol mixtures with a degree of         self-condensation of 1.5 to 10 such as, for example, technical         diglycerol mixtures with a diglycerol content of 40 to 50% by         weight;     -   methylol compounds such as, in particular, trimethylol ethane,         trimethylol propane, trimethylol butane, pentaerythritol and         dipenta-erythritol;     -   lower alkyl glucosides, particularly those containing 1 to 8         carbon atoms in the alkyl group, for example methyl and butyl         glucoside;     -   sugar alcohols containing 5 to 12 carbon atoms, for example         sorbitol or mannitol,     -   sugars containing 5 to 12 carbon atoms, for example glucose or         sucrose;     -   amino sugars, for example glucamine;     -   dialcoholamines, such as diethanolamine or         2-aminopropane-1,3-diol.         Preservatives

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the silver complexes known under the name of Surfacine® and the other classes of compounds listed in Appendix 6, Parts A and B of the Kosmetikverordnung (“Cosmetics Directive”).

Perfume Oils and Aromas

Suitable perfume oils are mixtures of natural and synthetic perfumes. Natural perfumes include the extracts of blossoms (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, orange), roots (nutmeg, angelica, celery, cardamom, costus, iris, calmus), woods (pinewood, sandalwood, guaiac wood, cedarwood, rosewood), herbs and grasses (tarragon, lemon grass, sage, thyme), needles and branches (spruce, fir, pine, dwarf pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials, for example civet and beaver, may also be used. Typical synthetic perfume compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Examples of perfume compounds of the ester type are benzyl acetate, phenoxyethyl isobutyrate, p-tert.butyl cyclohexylacetate, linalyl acetate, dimethyl benzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, ethylmethyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Ethers include, for example, benzyl ethyl ether while aldehydes include, for example, the linear alkanals containing 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxy-citronellal, lilial and bourgeonal. Examples of suitable ketones are the ionones, α-isomethylionone and methyl cedryl ketone. Suitable alcohols are anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons mainly include the terpenes and balsams. However, it is preferred to use mixtures of different perfume compounds which, together, produce an agreeable perfume. Other suitable perfume oils are essential oils of relatively low volatility which are mostly used as aroma components. Examples are sage oil, camomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime-blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, ladanum oil and lavendin oil. The following are preferably used either individually or in the form of mixtures: bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice, citrus oil, mandarin oil, orange oil, allylamyl glycolate, cyclovertal, lavendin oil, clary oil, β-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat. Suitable aromas are, for example, peppermint oil, spearmint oil, aniseed oil, Japanese anise oil, caraway oil, eucalyptus oil, fennel oil, citrus oil, wintergreen oil, clove oil, menthol and the like.

Dyes

Suitable dyes are any of the substances suitable and approved for cosmetic purposes as listed, for example, in the publication “Kosmetische Färbemittel” of the Farbstoffkommission der Deutschen Forschungs-gemeinschaft, Verlag Chemie, Weinheim, 1984, pages 81 to 106. Examples include cochineal red A (C.l. 16255), patent blue V (C.I. 42051), indigotin (C.I. 73015), chlorophyllin (C.I. 75810), quinoline yellow (C.I. 47005), titanium dioxide (C.I. 77891), indanthrene blue RS (C.I. 69800) and madder lake (C.I. 58000). Luminol may also be present as a luminescent dye. These dyes are normally used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.

The total percentage content of auxiliaries and additives may be from 1 to 50% by weight and is preferably from 5 to 40% by weight, based on the particular preparations. The preparations may be produced by standard hot or cold processes and are preferably produced by the phase inversion temperature method.

EXAMPLES Example 1

In a 500 ml three-necked flask equipped with a stirrer and reflux condenser, 3 g of agar agar were dissolved in 200 ml of water in boiling heat. First a homogeneous dispersion of 10 g of glycerol and 2 g of talcum in ad 100 g water and then a preparation of 25 g of chitosan (Hydagen® DCMF, 1% by weight in glycolic acid, Cognis, Düsseldorf/FRG), 5 g of an aqueous 10% by weight extract of Vaccinium myrtillus, 3 g of an aqueous 10% by weight extract of Trifolium pratense, 1 g ascorbic acid, 0.5 g of Phenonip® (preservative mixture containing phenoxyethanol and parabens) and 0.5 g of Polysorbate-20 (Tween® 20, ICI) in ad 100 g water were then added to the mixture over a period of about 30 mins. with vigorous stirring. The matrix obtained was filtered, heated to 60° C. and added dropwise to a 0.5% by weight sodium alginate solution. An aqueous preparation containing 8% by weight microcapsules with a mean diameter of 1 mm was obtained after sieving.

Example 2

In a 500 ml three-necked flask equipped with a stirrer and reflux condenser, 3 g of agar agar were dissolved in 200 ml of water in boiling heat. First a homogeneous dispersion of 10 g of glycerol and 2 g of talcum in ad 100 g water and then a preparation of 25 g of chitosan (Hydagen® DCMF, 1% by weight in glycolic acid, Cognis, Düsseldorf/FRG), 5 g of an aqueous 10% by weight extract of Vaccinium myrtillus, 3 g of an aqueous 10% by weight extract of Trifolium pratense, 1 g tocopherol, 0.5 g Phenonip® (preservative mixture containing phenoxyethanol and parabens) and 0.5 g Polysorbate-20 (Tween® 20, ICI) in ad 100 g water were added to the mixture over a period of about 30 mins. with vigorous stirring. The matrix obtained was filtered, heated to 50° C and dispersed with vigorous stirring in 2.5 times its volume of paraffin oil cooled beforehand to 15° C. The dispersion was then washed with an aqueous solution containing 1% by weight of sodium lauryl sulfate and 0.5% by weight of sodium alginate and then repeatedly with a 0.5% by weight aqueous Phenonip solution, the oil phase being removed in the process. An aqueous preparation containing 8% by weight of microcapsules with a mean diameter of 1 mm was obtained after sieving.

Example 3

In a 500 ml three-necked flask equipped with a stirrer and reflux condenser, 3 g of agar agar were dissolved in 200 ml of water in boiling heat. First a homogeneous dispersion of 10 g of glycerol and 2 g of talcum in ad 100 g water and then a preparation of 25 g of chitosan (Hydagen® DCMF, 1% by weight in glycolic acid, Cognis, Düsseldorf/FRG), 5 g of an aqueous 10% by weight extract of Vaccinium myrtillus, 3 g of an aqueous 10% by weight extract of Vitis vinifera, 0.5 g tocopherol, 0.5 g ascorbic acid, 0.5 g of Phenonip® (preservative mixture containing phenoxyethanol and parabens) and 0.5 g of Polysorbate-20 (Tween® 20, ICI) in ad 100 g water were then added to the mixture over a period of about 30 mins. with vigorous stirring. The matrix obtained was filtered, heated to 60° C. and added dropwise to a 15% by weight Sodium Laureth Sulfate. An aqueous preparation containing 9% by weight microcapsules with a mean diameter of 1 mm was obtained after sieving.

Example 4

In a 500 ml three-necked flask equipped with a stirrer and reflux condenser, 3 g of agar agar were dissolved in 200 ml of water in boiling heat. First a homogeneous dispersion of 10 g of glycerol and 2 g of talcum in ad 100 g water and then a preparation of 25 g of chitosan (Hydagen® DCMF, 1% by weight in glycolic acid, Cognis, Düsseldorf/FRG), 5 g of an aqueous 10% by weight extract of Trifolium pratense, 3 g of an aqueous 10% by weight extract of Vitis vinifera, 0.5 g tocopherol, 0.5 g ascorbic acid, 0.5 g Phenonip® (preservative mixture containing phenoxyethanol and parabens) and 0.5 g Polysorbate-20 (Tween® 20, ICI) in ad 100 g water were added to the mixture over a period of about 30 mins. with vigorous stirring. The matrix obtained was filtered, heated to 60° C. and added dropwise to a 15% by weight solution of sodium pyrophosphate. An aqueous preparation containing 8% by weight of microcapsules with a mean diameter of 1 mm was obtained after sieving.

Example 5

In a 500 ml three-necked flask equipped with a stirrer and reflux condenser, 3 g of agar agar were dissolved in 200 ml of water in boiling heat. First a homogeneous dispersion of 10 g of glycerol and 2 g of talcum in ad 100 g water and then a preparation of 25 g of chitosan (Hydagen® DCMF, 1% by weight in glycolic acid, Cognis, Düsseldorf/FRG), 5 g of an aqueous 10% by weight extract of Trifolium pratense, 3 g of an aqueous 10% by weight extract of Thea vinensis, 0.5 g tocopherol, 0.5 g ascorbic acid, 0.5 g Phenonip® (preservative mixture containing phenoxyethanol and parabens) and 0.5 g Polysorbate-20 (Tween® 20, ICI) in ad 100 g water were added to the mixture over a period of about 30 mins. with vigorous stirring. The matrix obtained was filtered, heated to 50° C. and dispersed with vigorous stirring in 2.5 times its volume of paraffin oil cooled beforehand to 15° C. The dispersion was then washed with a 15% by weight sodium pyrophosphate solution and then repeatedly with a 0.5% by weight aqueous Phenonip solution, the oil phase being removed in the process. An aqueous preparation containing 10% by weight of microcapsules with a mean diameter of 1 mm was obtained after sieving.

Example 6

In a 500 ml three-necked flask equipped with a stirrer and reflux condenser, 3 g of gelatin were dissolved in 200 ml of water in boiling heat. First a homogeneous dispersion of 10 g of glycerol and 2 g of talcum in ad 100 g water and then a preparation of 25 g of chitosan (Hydagen® DCMF, 1% by weight in glycolic acid, Cognis, Düsseldorf/FRG), 3 g of an aqueous 10% by weight extract of Vaccinium myrtillus, 2 g of an aqueous 10% by weight extract of Trifolium pratense, 3 g of an aqueous 10% by weight extract of Vitis vinifera, 0.5 g tocopherol, 0.5 g ascorbic acid and 0.5 g Phenonip® in ad 100 g water were added to the mixture over a period of about 30 mins. with vigorous stirring. The matrix obtained was filtered, heated to 60° C. and added dropwise to a 0.5% by weight solution of Hydagen® SCD (succinylated chitosan, Cognis). An aqueous preparation containing 8% by weight of microcapsules with a mean diameter of 1 mm was obtained after sieving.

Example 7

In a 500 ml three-necked flask equipped with a stirrer and reflux condenser, 3 g of agar agar were dissolved in 200 ml of water in boiling heat. First a homogeneous dispersion of 10 g of glycerol and 2 g of talcum in ad 100 g water and then a preparation of 25 g of chitosan (Hydagen® DCMF, 1% by weight in glycolic acid, Cognis, Dusseldorf/FRG), 3 g of an aqueous 10% by weight extract of Vaccinium myrtillus, 2 g of an aqueous 10% by weight extract of Trifolium pratense, 3 g of an aqueous 10% by weight extract of Vitis vinifera, 0.5 g tocopherol, 1 g of an aqueous 10% by weight extract of Thea vinensis, 0.5 g tocopherol, 0.5 g ascorbic acid, 0.5 g Phenonip® (preservative mixture containing phenoxyethanol and parabens) and 0.5 g Polysorbate-20 (Tween® 20, ICI) in ad 100 g water were added to the mixture over a period of about 30 mins. with vigorous stirring. The matrix obtained was filtered, heated to 60° C. and added dropwise to a 0.5% by weight sodium alginate solution. To obtain microcapsules of the same diameter, the preparations were then sieved.

Example 8

10 g of a freeze-dried extract of Vaccinium myrtillus, 10 g of a freeze-dried extract of Trifolium pratense, 5 g of a freeze-dried extract of Vitis vinifera, 2 g tocopherol and 2 g ascorbic acid were introduced into a stirred vessel. 100 g of a 20% by weight solution of soybean lecithin in propylene glycol were then added. The mixture was heated to 65° C. and stirred until a homogeneous, clear solution was obtained.

Example 9

10 g of a freeze-dried extract of Vaccinium myrtillus, 10 g of a freeze-dried extract of Trifolium pratense, 5 g of a freeze-dried extract of Vitis vinifera, 5 g of a freeze-dried extract of Thea vinensis, 2 g tocopherol and 2 g ascorbic acid were introduced into a stirred vessel. 100 g of a 20% by weight solution of soybean lecithin in propylene glycol were then added. The mixture was heated to 65° C. and stirred until a homogeneous, clear solution was obtained.

A number of Formulation Examples for cosmetic preparations are presented in Table 1 below. TABLE 11 Examples for cosmetic preparations (water, preservative to 100% by weight) Composition (INCI) 1 2 3 4 5 6 7 8 9 10 Emulgade ® SE 5.0 5.0 4.0 — — 5.0 5.0 4.0 — — Glyceryl Sterate (and) Ceteareth 12/20 (and) Cetearyl Alcohol (and) Cetyl Palmitate Eumulgin ® B1 — — 1.0 — — — — 1.0 — — Ceteareth-12 Lameform ® TGI — — — 4.0 — — — — 4.0 — Polyglyceryl-3 Isostearate Dehymuls ® PGPH — — — — 4.0 — — — — 4.0 Polyglyceryl-2 Dipolyhydroxystearate Monomuls ® 90-O 18 — — — 2.0 — — — — 2.0 — Glyceryl Oleate Cetiol ® HE — — — — 2.0 — — — — 2.0 PEG-7 Glyceryl Cocoate Cetiol ® OE — — — 5.0 6.0 — — — 5.0 6.0 Dicaprylyl Ether Cetiol ® PGL — — 3.0 10.0  9.0 — — 3.0 10.0  9.0 Hexyldecanol (and) Hexyldecyl Laurate Cetiol ® SN 3.0 3.0 — — — 3.0 3.0 — — — Cetearyl Isononanoate Cetiol ® V 3.0 3.0 — — — 3.0 3.0 — — — Decyl Oleate Myritol ® 318 — — 3.0 5.0 5.0 — — 3.0 5.0 5.0 Coco Caprylate Caprate Bees Wax — — — 7.0 5.0 — — — 7.0 5.0 Nutrilan ® Elastin E20 2.0 — — — — 2.0 — — — — Hydrolyzed Elastin Nutrilan ® I-50 — 2.0 — — — — 2.0 — — — Hydrolyzed Collagen Gluadin ® AGP — — 0.5 — — — — 0.5 — — Hydrolyzed Wheat Gluten Gluadin ® WK — — — 0.5 0.5 — — — 0.5 0.5 Sodium Cocoyl Hydrolyzed Wheat Protein Euperlan ® PK 3000 AM — — — — — — — — — — Glycol Distearate (and) Laureth-4 (and) Cocamidopropyl Betaine Arlypon ® F — — — — — — — — — — Laureth-2 Microcapsules 1.0 1.0 1.0 1.0 1.0 2.0 2.0 2.0 2.0 2.0 of Example 7 Hydagen ® CMF 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Chitosan Magnesium Sulfate Hepta Hydrate — — — 1.0 1.0 — — — 1.0 1.0 Glycerin (86% by weight) 3.0 3.0 5.0 5.0 3.0 3.0 3.0 5.0 5.0 3.0 Composition (INCI) 11 12 13 14 15 16 17 18 19 20 Dehymuls ® PGPH 4.0 3.0 — 5.0 — — — — — — Polyglyceryl-2 Dipolyhydroxystearate Lameform ® TGI 2.0 1.0 — — — — — — — — Polyglyceryl-3 Diisostearate Emulgade ® PL 68/50 — — — — 4.0 — — — 3.0 — Cetearyl Glucoside (and) Cetearyl Alcohol Eumulgin ® B2 — — — — — — — 2.0 — — Ceteareth-20 Tegocare ® PS — — 3.0 — — — 4.0 — — — Polyglyceryl-3 Methylglucose Distearate Eumulgin VL 75 — — — — — 3.5 — — 2.5 — Polyglyceryl-2 Dipolyhydroxystearate (and) Lauryl Glucoside (and) Glycerin Bees Wax 3.0 2.0 5.0 2.0 — — — — — — Cutina ® GMS — — — — — 2.0 4.0 — — 4.0 Glyceryl Stearate Lanette ® O — — 2.0 — 2.0 4.0 2.0 4.0 4.0 1.0 Cetearyl Alcohol Antaron ® V 216 — — — — — 3.0 — — — 2.0 PVP/Hexadecene Copolymer Myritol ® 818 5.0 — 10.0  — 8.0 6.0 6.0 — 5.0 5.0 Cocoglycerides Finsolv ® TN — 6.0 — 2.0 — — 3.0 — — 2.0 C12/15 Alkyl Benzoate Cetiol ® J 600 7.0 4.0 3.0 5.0 4.0 3.0 3.0 — 5.0 4.0 Oleyl Erucate Cetiol ® OE 3.0 — 6.0 8.0 6.0 5.0 4.0 3.0 4.0 6.0 Dicaprylyl Ether Mineral Oil — 4.0 — 4.0 — 2.0 — 1.0 — — Cetiol ® PGL — 7.0 3.0 7.0 4.0 — — — 1.0 — Hexadecanol (and) Hexyldecyl Laurate Bisabolol 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Microcapsules 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 of Example 9 Hydagen ® CMF 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Chitosan Neo Heliopan ® Hydro 3.0 — — 3.0 — — 2.0 — 2.0 — Sodium Phenylbenzimidazole Sulfonate Neo Heliopan ® 303 — 5.0 — — — 4.0 5.0 — — 10.0  Octocrylene Neo Heliopan ® BB 1.5 — — 2.0 1.5 — — — 2.0 — Benzophenone-3 Neo Heliopan ® E 1000 5.0 — 4.0 — 2.0 2.0 4.0 10.0  — — Isoamyl p-Methoxycinnamate Neo Heliopan ® AV 4.0 — 4.0 3.0 2.0 3.0 4.0 — 10.0  2.0 Octyl Methoxycinnamate Uvinul ® T 150 2.0 4.0 3.0 1.0 1.0 1.0 4.0 3.0 3.0 3.0 Octyl Triazone Zinc Oxide — 6.0 6.0 — 4.0 — — — — 5.0 Titanium Dioxide — — — — — — — 5.0 — — Glycerin (86% by weight) 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 (1, 6) Soft cream, (2, 3, 7, 8) Moisturizing emulsion, (4, 5, 9, 10) Night cream (11) W/O sun protection cream, (12-14) W/O sun protection lotion, (15, 18, 20) O/W sun protection lotion, (16, 17, 19) O/W sun protection cream 

1-22. (canceled)
 23. An antioxidative composition comprising: (a) an active component selected from the group consisting of (i) at least two extracts selected from the group consisting of Vaccinium myrtillus, Trifolium pratense, Vitis vinifera and Thea vinensis; (ii) at least two active components selected from the group consisting of anthocyanosides, isoflavone glucosides and polyphenols; and (iii) mixtures thereof; and (b) a co-active component selected from the group consisting of tocopherol, ascorbic acid and mixtures thereof.
 24. The composition of claim 23 wherein (a) and (b) are employed in a ratio by weight of from about 1:9 to 9:1.
 25. The composition of claim 23 wherein (a) and (b) further comprise a substance selected from the group consisting of lecithins, phospholipids and mixtures thereof.
 26. Microcapsules containing the antioxidative composition of claim
 23. 27. The microcapsules of claim 26 wherein the microcapsules have a mean diameter of from about 0.1 to 5 mm.
 28. The microcapsules of claim 26 wherein the microcapsules comprise a membrane and a matrix containing the antioxidative composition.
 29. The microcapsules of claim 26 wherein the microcapsules are produced by preparing a matrix, optionally dispersing the matrix in an oil phase, dispersing the matrix in a solution selected from the group consisting of an aqueous anionic polymer solution and an aqueous chitosan solution and optionally removing the oil phase.
 30. The microcapsules of claim 29 wherein the matrix contains: (i) gel formers; (ii) an ingredient selected from the group consisting of anionic polymers, chitosans and mixtures thereof; and (iii) (a)+(b).
 31. A process for treating human skin comprising orally ingesting or topically administering onto the skin an antioxidative composition containing: (a) an active component selected from the group consisting of (i) at least two extracts selected from the group consisting of Vaccinium myrtillus, Trifolium pratense, Vitis vinifera and Thea vinensis; (ii) at least two active components selected from the group consisting of anthocyanosides, isoflavone glucosides and polyphenols; and (iii) mixtures thereof; and (b) a co-active component selected from the group consisting tocopherol, ascorbic acid and mixtures thereof.
 32. The process of claim 31 wherein (a) and (b) are employed in a ratio by weight of from about 1:9 to 9:1.
 33. The process of claim 31 wherein (a) and (b) further comprise a substance selected from the group consisting of lecithins, phospholipids and mixtures thereof.
 34. The process of claim 31 wherein the antioxidative composition is administered in the form of microcapsules.
 35. The process of claim 34 wherein the microcapsules have a mean diameter of from about 0.1 to 5 mm.
 36. The process of claim 34 wherein the microcapsules comprise a membrane and a matrix containing the antioxidative composition.
 37. The process of claim 34 wherein the microcapsules are produced by preparing a matrix, optionally dispersing the matrix in an oil phase, dispersing the matrix in a solution selected from the group consisting of an aqueous anionic polymer solution and an aqueous chitosan solution and optionally removing the oil phase.
 38. The process of claim 37 wherein the matrix contains: (i) gel formers; (ii) an ingredient selected from the group consisting of anionic polymers, chitosans and mixtures thereof; and (iii) (a)+(b). 